Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Method for Aerogel Production and an Aerogel Composite Material
Field of the Invention
The present invention relates to a method for producing an aerogel according
to the preamble
of claim 1 and a composite material obtainable by this method as a high-
performance
insulation material.
Prior art
Aerogels have a low density and a high porosity with open pores in the range
of < 50 nm and a
large internal surface area. This results in a low coefficient of thermal
conductivity. Accordingly,
aerogels are also suitable as thermal insulation materials. However, the high
porosity also
results in a low mechanical stability of the aerogel.
Therefore, in recent years, composite materials made of fiber materials and
aerogels have been
proposed. Such composite materials may be used as insulation materials, for
example.
WO 93/06044, for example, discloses a method for producing an aerogel matrix
composite
material in the following method steps:
¨ Production of an aerogel precursor,
¨ Mixing the aerogel precursor with fibers,
¨ Aging the aerogel precursor containing the fibers to produce a gel,
¨ Immersing the gel in a solvent suitable for supercritical drying, and
¨ Drying the gel under supercritical conditions.
Glass fibers or rock wool fibers, among others, are suitable as fibers that
can be embedded in
an aerogel. However, the method that is described has the disadvantage that
the gel must be
dried under supercritical conditions, so that an autoclave is necessary and
there must usually be
at least one solvent replacement. This is a very complicated and time-
consuming procedure.
Drying requires a special equipment expense (pressurized reactor for critical
point drying; for
example, CO2 at > 74 barh 30 C). Accordingly, supercritical drying of aerogels
is suitable only
for small batches and on a laboratory scale.
Because of the complexity of supercritical drying of gels, a method has been
developed by
which even subcritical drying of the gel at temperatures below 150 C is
possible with a
circulating air stream under normal pressure. In subcritical drying of a gel,
the free SiOH groups
of the resulting gel should first be deactivated for further condensation.
This takes place, for
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example, by adding trimethylchlorosilane to the gel (see F. Schwertfeger, D.
Frank, M. Schmidt,
"Hydrophobic water glass-based aerogels without solvent exchange or
supercritical drying" in
Journal of Non-Crystalline Solids, 225 (1998), pp. 24-29). The
trimethylchlorosilane here reacts
with the OH groups of the silicate surface of the gel, splitting off HCI. Due
to the
hydrophobization of the silicate surface, water is displaced out of the pores
in the gel.
Hexamethyldisiloxane and excess trimethylchlorosilane form the organic phase
and remain in
the pores of the gel. The resulting hydrochloric acid first saturates the
aqueous phase and then
escapes into the gas phase at higher concentration.
However, the method described here has the disadvantage that it cannot be used
in
combination with rock wool fibers because the hydrochloric acid that is
released partially
dissolves the rock wool fibers. Rock wool consists of at least 52 wt% acid
soluble fractions
(metal oxides such as A1203, CaO, MgO and Fe203). For this reason, the
aerogels based on glass
wool that are currently being used are sufficiently stable at an acidic pH, on
the one hand, but
have an inadequate thermal stability in the event of a fire, on the other
hand.
WO 94/25149 describes a method for producing a highly porous xerogel in which
the surface of
the gel is hydrophobized with surface-modifying compounds in order to reduce
the capillary
pressure in the pores of the gel before drying so that the gel will not
collapse in the subsequent
drying step. This method consists of a sequence of aging, washing, and drying
steps. The
method that is described is very complex because the gel must be washed with
aprotic solvents
before and after hydrophobizing with trimethylchlorosilane. The hydrochloric
acid which is
released in hydrophobizing and would attack rock wool fibers, for example, is
also a
disadvantage.
DE-OS-196 48 798 describes a method for producing organically modified
aerogels by surface
modification of the aqueous gel (without prior solvent replacement) and then
drying.
Preferably hexamethyldisiloxane (HMDSO) is used as the silylating agent. In
addition, a base or
acid may also be present as the catalyst in the hydrophobizing reaction.
Preferred acids include hydrochloric, sulfuric, phosphoric, hydrofluoric,
oxalic, acetic or formic
acid, but hydrochloric acid is preferred. Before drying, the silylated gel may
optionally be
washed with a protic or aprotic solvent. According to the teaching of DE-OS-
196 48 798, the gel
that is formed is preferably dried under uncritical conditions. Since the use
of organic solvents
is completely omitted according to the teaching of DE-OS-196 48 798, all the
SiOH groups that
can be reached by the silylating agent that is used can react with the
silylating agent. Therefore,
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according to DE-OS 196 48 798, a very high degree of coverage of the internal
surface of the
hydrogel can be achieved.
WO 2013/053951 discloses a method for producing a xerogel with a coefficient
of thermal
conductivity between 5 and 25 mW/mK, in which in a first process step a sol is
poured into a
reactor in which a fibrous reinforcing material has previously been arranged.
The sol is then
gelled, aged and hydrophobized. Next the hydrophobized alcogel is first
predried at
temperatures up to 80 C and then completely dried under subcritical conditions
and
temperatures > 100 C and preferably between 120 C and 140 C until the residual
alcohol
content is < 3%. All process steps except for the process step mentioned last
can be carried out
in the same reactor. It is important that the inside walls 10 are a distance
of 70 mm or less from
one another. If greater wall distances are selected, then the fiber-reinforced
xerogels thereby
produced will have a coefficient of thermal conductivity of > 25 mW/Km.
The alcogel formed in the second process step has an alcohol content between
15 wt% and
90 wt% relative to the weight of the original sol. The hydrophobization
preferably with HMDSO
(hexamethyldisiloxane) takes place in the presence of hydrochloric acid at a
pH between 1 and
3. Formic acid is proposed as an alternative for the use of hydrochloric acid.
US patent no. 5,746,992 relates to the production of a silicon aerogel. In
this production
process the alcohol is removed from the alcogel under subcritical conditions.
According to one
exemplary embodiment, the hydrolysis of tetraethoxysilane takes place in two
steps. In a first
step, the tetraethoxysilane, methanol, some water and nitric acid are mixed
together in a class
container, then the glass container is sealed and kept at 60 C for 24 hours.
During this time the
tetraethoxysilane partially hydrolyzes under acidic conditions. Then the
mixture is adjusted to a
basic pH by adding an aqueous/alcoholic ammonia solution and kept again at 60
C for 24 hours
to achieve a secondary hydrolysis under basic conditions. Under these
conditions, a clear silicic
acid gel is obtained, having an internal porosity of 74% after drying in an
oven. According to
US 5,746,992 no hydrophobization of the gel is provided.
WO 2015/014813 discloses a method for producing an aerogel material similar to
that of
WO 2013/053951. As already described in WO 2013/053951, an alcogel is first
produced in an
alcoholic medium and then allowed to react with an activatable, acid-catalyzed
hydrophobizing
agent, namely HMDSO in the present case. What is novel about this in
comparison with
WO 2012/053951 is that the hydrophobizing agent HMDSO Is already added to the
silicon oxide
sol in the first process step. The amount of the hydrophobizing agent in the
sol here amounts to
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3 to 80% by volume. This is activated only by forming the gel, which may
optionally also be
aged, by the release or addition of at least one hydrophobization catalyst
that works together
with the hydrophobizing agent.
WO 2015/014813 describes one exemplary embodiment for producing granules,
characterized
in that the gel that has been formed and aged is pulverized mechanically, then
transferred to a
closed pressurized container and hydrophobized by means of HCI in the presence
of HMDSO,
then predried on a conveyor belt at 50 C and finally dried completely at 150
C.
In another example, an aerogel insulation sheet is produced by mixing an
alcoholic solution
with a polyethoxydisiloxane sol with a 22% Si02 content and HMDSO with a slow-
release agent
doped with 10% HCI. After adding an ammonia solution, the thoroughly mixed sol
is poured
into a mold which had previously been lined with a polyester nonwoven fiber
matte. After aging
for 5 hours, the gel sheet is lifted up from the mold and stored in a closed
vessel for 24 hours at
65 C and hydrophobized. At this temperature, HCI escapes from the
microencapsulation and
activates the HMDSO that is present. The vessel is then opened and the gel
sheet is first dried
at 50 C and then at 130 C.
Object of the Invention
The object of the present invention is to propose a method for aerogel
production that can be
carried out as inexpensively as possible. In addition, the method should
permit production of an
aerogel material on an industrial scale in the most environmentally friendly
way possible. The
aerogel material (not including a fiber matrix) should have a porosity of >
80%, preferably
> 90%, especially preferably > 92%, and a density of < 0.2 g/mL, preferably
0.15 g/mL, and
especially preferably < 0.12 g/mL. Another goal is for supercritical drying of
the aerogel material
to be unnecessary in production. Another goal is to provide an aerogel
composite material,
which may also contain acid-sensitive fibers, for example, rock wool fibers.
One goal is to make
available a fiber-aerogel composite material with a coefficient of thermal
conductivity X of
<20 mW/mK, preferably < 18 mW/mK, which can be produced on an industrial
scale.
Description
The invention relates to a method for producing an aerogel in which a
silicatic sol is first
prepared by hydrolyzing an organosilane compound, e.g., tetraethoxysilane
(TEOS) under acidic
or basic conditions, then producing a gel by adding a base to the sol and next
aging the
resulting gel. After aging, the gel is hydrophobized with a silylation agent
in the presence of an
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acid as the catalyst, and then the gel is dried, preferably by subcritical
drying. For production of
the aerogel or xerogel, essentially the same processes and parameters may be
used as those
described in WO 2013/053951 or WO 2015/014813.
Within the scope of the present invention, aerogels should be understood to be
highly porous
solids, in particular those based on silicate, regardless of the drying
method. The term "aerogel"
is understood to be a highly porous material with air as the dispersant in
this sense.
According to the invention, the object is achieved by a method according to
the preamble of
claim 1 by using hexamethyldisiloxane as the hydrophobizing agent and nitric
acid (HNO3) as
the acid. The process according to the invention has the great and surprising
advantage that the
hydrophobization in the presence of nitric acid produces highly porous stable
aerogels with
excellent low thermal conductivities. In particular aerogels with a porosity
of < 90%, preferably
> 92% and with a coefficient of thermal conductivity of < 18 mW/mK can be
produced on an
industrial scale with the process according to the invention.
The silicatic sol is advantageously prepared by hydrolysis of alkoxysilanes or
hydroxyalkoxysilanes, preferably from tetraethoxysilane (TEOS) or
trimethylchlorosilane. Use of
TEOS has the advantage that it is soluble in alcohol, e.g., Et0H. Accordingly,
the sol can be
prepared in alcohol, an alcoholic or alcohol-containing solvent mixture, which
is advantageous
for the process because then there is less water in the pores of the gel which
is formed later. An
alcoholic solvent mixture should be understood to be a mixture in which
alcohol is the main
ingredient, preferably in a volume amount of > 90 vol% and especially
preferably > 95 vol%. On
the other hand, an alcohol-containing solvent mixture should be understood to
be one in which
the percentage volume amount of the alcohol(s) is < 50 vol% and preferably <
40 vol%.
The sol is advantageously prepared in an acidic medium by hydrolysis of
tetraethoxysilane
(TEOS) which is placed in a solvent preferably Et0H. Preferably hydrochloric
acid or formic acid
is used for the hydrolysis. According to a particularly advantageous process
variant, a
prehydrolyzed sol is used. This makes it possible to greatly shorten the
process of production of
the gel. Prehydrolyzed sols are stable and can be stored and are also
commercially available.
Prehydrolyzed sols which are present in an amount between 5% and 30% (w/w)
SiO2 and
preferably between 10% and 25% (w/w) Si02 in alcohol, preferably Et0H, are
used.
The pH in hydrophobization is advantageously set at a value between 1 and 7,
preferably
between 2 and 5. In the acidic range at approx. pH 2, HMDSO reacts rapidly
with the SiOH
groups that are still free.
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The pH in hydrophobization is advantageously set at a value between 0.2 and 5,
preferably
between 0.5 and 3 and especially preferably between 0.8 and 2. The pH is
measured in the
aqueous phase. Such a pH is advantageously compatible with rock wool fibers
when using nitric
acid as the hydrophobization catalyst.
The gelation expediently takes place in a temperature interval between 30 C
and 80 C,
preferably between 50 C and 75 C and especially preferably between 60 C and 70
C. For
gelation of the sol, a base, e.g., ammonia in the form of an aqueous ammonia
solution, is added
to the mixture.
The hydrolysis, gelation and hydrophobization are advantageously carried out
in an essentially
alcoholic solvent, preferably Et0H, where the water content is expediently <
20 vol%,
preferably < 10 vol% and especially preferably < 5 vol%. It has been found
that a low water
content has a positive effect on the quality of the aerogel produced.
For the production of a fiber composite material, fibers may be added before
and/or during the
production of the gel. The fibers are preferably added before the actual
gelatin (condensation),
i.e., the fibers and the sol are preferably mixed together between steps a)
and b). Rock wool
fibers are especially used advantageously. These have the great advantage that
they are
practically nonflammable.
By optimizing the individual process steps it is surprisingly possible to
carry out the
hydrophobization without prior solvent replacement. This has the major
advantage that on the
one hand the process proceeds more rapidly, while on the other hand smaller
amounts of
solvent are consumed.
It is fundamentally conceivable to add the silylation agent already in process
step a). This is
possible, for example, when a silylation agent that is stable in an alkaline
medium is used and
the sol preparation and gelation take place in the alkaline medium. HMDSO, for
example, is a
suitable silylation agent that is stable in an alkaline medium.
The subject matter of the present invention is also an aerogel, in particular
a xerogel obtainable
by
a) Preparing a sol,
b) Producing and optionally aging the gel,
c) Hydrophobizing the gel with a silylating agent in the presence of an
acid as
catalyst and
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d) Drying the gel,
characterized in that
e) Hexamethyldisiloxane is used as the hydrophobizing agent and nitric acid
(HNO3)
is used as the acid.
Additional advantageous properties of the gel have already been explained in
the discussion of
the production process.
Another subject matter of the present invention is an aerogel fiber composite
material
obtainable by mixing the sol prepared according to the method described here
with mineral
fibers, in particular rock wool fibers. The aerogel composite material has a
porosity of > 90%
and a coefficient of thermal conductivity of < 18 mW/mK. The mineral fibers
are surprisingly
not dissolved to any significant extent during this production process. In
particular because of
the known acid sensitivity of rock wool fibers it could not have been expected
that the
hydrophobization treatment could be carried out successfully under acidic
conditions.
Although fundamentally glass wool fibers could also be used to produce the
composite
material, rock wool fibers are preferred. Rock wool fibers have the advantage
over glass wool
fibers that their fire resistance is much better.
Additionally, the subject matter of the present invention is a composite
material in the form of
an insulation sheet consisting of the aerogel and mineral fibers according to
the invention.
The invention is described in greater detail below on the basis of the
following exemplary
embodiments.
Production of an aerogel
Starting with 122 L ethanol (abs. and denatured with 2% methyl ethyl ketone
(MEK)), 47 L TEOS
(98%) are then added. The mixture is then heated to approx. 50 C. Next 14 L
oxalic acid solution
(2.44 g = 0.0193 mol) is added while stirring. For the hydrolysis, the
solution is stirred for about
24 hours at 50 C, then the mixture is allowed to cool to 45 C and 36.5 mL
NH4OH solution (28-
30%) in 8 L water (= 0.07M) is added. Next the mixture is left to stand for
approx. 24 hours
(without stirring). Gelation occurs during this period of time. Next the gel
is optionally washed
dynamically once or twice with heptane and then hydrophobized (see below). The
subsequent
hydrophobization also takes place dynamically by recirculating the silylating
agent (approx.
15 hours at approx. 60 C). As soon as hydrophobization is concluded, the
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solvent/hydrophobizing agent mixture is drained out, processed and later
reused in the next
production process.
Hydrophobization of a lyogel with trimethylsilyl chloride
Reaction of the lyogel under acidic conditions, which leads to the
decomposition of rock wool:
1.6 g lyogel (from 7% Si02 tetraethyl orthosilicate with rock wool) was
combined with 10 mL
trimethylsilyl chloride. The rock wool disintegrates overnight to form a
yellowish fibrous and
mechanically unstable substance. Composite materials prepared in this way are
hydrophobic,
highly porous and float on water.
Hydrophobization experiments with HMDSO using various organic and inorganic
acids as
catalysts
Various organic and inorganic acids, e.g., sulfuric acid (H2SO4), hydrochloric
acid (HCI),
phosphoric acid (H3PO4), oxalic acid, formic acid and acetic acid were used as
the
hydrophobization catalysts. In all these experiments, the resulting aerogel
rock wool fiber
composite material had a "vitreous" (transparent) appearance and a few or many
fissures. In
some samples, a definite shrinkage was also observed after drying. The
measured coefficient of
thermal conductivity values varied in the range above 20 mW/mK and were
therefore
unsatisfactory in view of the requirements of a high-performance insulation
material.
According to the experience of the inventors, based on a number of
experiments, samples (rock
wool fiber matrix and aerogel), which appear to be vitreous and/or undergo
shrinkage in drying
have a much higher coefficient of thermal conductivity than those which appear
to be
"translucent" or "milky" and have practically no fissures and do not shrink
when dried. Samples
with a conductivity value between 16 and 18 mW/mK have a blue cast and
practically no
fissures.
The coefficient of thermal conductivity was determined according to the EN
12667 standard
(standard hot plate method) at 20 C and normal pressure.
Production of the aerogel fiber composite material
55 L of a prehydrolyzed sol (75% prehydrolyzed; 20% (w/w) Si02 content) in
Et0H (abs.) is
mixed with slightly more than twice that amount of ethanol (130 L) and
homogenized while
stirring. At the same time, the mixture is heated to approx. 45 C. As soon as
the temperature
has been established and the mixture is homogenized, an aqueous NH4OH solution
(approx. 6 L;
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0.55M) is then added to the sol, homogenized briefly and next transferred to a
container that
already holds a fiber matrix equipped with a temperature sensor. Next the
contents of the
container are heated to approx. 65 C and the mixture is left to stand for
aging. The aging of the
gel takes place between 24 and 120 hours, preferably between 48 and 96 hours
and especially
preferably for approx. 72 hours.
After gelation, the gel is hydrophobized dynamically in the same container by
adding an excess
of HMDSO (in the present case approx. 270 L of a 20 to 98% (w/w) HMDSO
solution) and
approx. 5 L of an essentially alcoholic HNO3 solution (approx. 4 to 7% w/w)
for 24 hours at 75 C,
i.e., by circulating the liquid phase.
After cooling, the partially spent hydrophobizing solution is transferred to a
mixer/settler and
the prepared aerogel fiber composite material is dried in a circulating air
oven for 2 to 5 hours
at approx. 150 C.
Water is added to the partially spent hydrophobizing solution (approx. 10% of
the volume of
the hydrophobizing solution) in the mixer/settler and the mixture is stirred
intensely for 10 to
30 minutes. Then the mixture is left to stand overnight, whereupon an aqueous
phase
separates at the bottom. The aqueous phase is separated and discarded. The
alcoholic
hydrophobizing solution can then be reused in the next batch, optionally after
being
concentrated with HMDSO.
The present invention relates to a method for producing aerogel and a
composite material
produced by means of this method from an aerogel and mineral fibers. An
aerogel material
produced on the basis of silicate with a coefficient of thermal conductivity
coefficient of
<18 mW/mK can be obtained by hydrophobizing the aerogel material with HMDSO in
the
presence of nitric acid.
